Daniels Brian S, Hou Xintong, Corio Stephanie A, Weissman Lindsey M, Dong Vy M, Hirschi Jennifer S, Nie Shaozhen
Department of Chemistry, University of California, Irvine, 92697, Irvine, CA, USA.
Department of Chemistry, Binghamton University, 13902, Binghamton, NY, USA.
Angew Chem Int Ed Engl. 2023 Sep 4;62(36):e202306511. doi: 10.1002/anie.202306511. Epub 2023 Jul 21.
We describe a copper catalyst that promotes the addition of phosphines to cyclopropenes at ambient temperature. A range of cyclopropylphosphines bearing different steric and electronic properties can now be accessed in high yields and enantioselectivities. Enrichment of phosphorus stereocenters is also demonstrated via a Dynamic Kinetic Asymmetric Transformation (DyKAT) process. A combined experimental and theoretical mechanistic study supports an elementary step featuring insertion of a Cu -phosphido into a carbon-carbon double bond. Density functional theory calculations reveal migratory insertion as the rate- and stereo-determining step, followed by a syn-protodemetalation.
我们描述了一种在室温下促进膦加成到环丙烯上的铜催化剂。现在可以以高产率和对映选择性获得一系列具有不同空间和电子性质的环丙基膦。还通过动态动力学不对称转化（DyKAT）过程证明了磷立体中心的富集。一项结合实验和理论的机理研究支持了一个基本步骤，即铜磷化物插入碳-碳双键。密度泛函理论计算表明迁移插入是速率和立体化学决定步骤，随后是顺式质子脱金属化。
